Alkyl lactone-derived corrosion inhibitors

ABSTRACT

Disclosed are alkyl lactone-derived hydroxyamide and alkyl lactone-derived hydroxyester used in compositions and methods for inhibiting corrosion. The alkyl lactone-derived hydroxyamide and alkyl lactone-derived hydroxyester are reaction products of an alkyl lactone and an amine, and an alkyl lactone and an alcohol, respectively.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 62/697,165, filed Jul. 12, 2018, the disclosure ofwhich is incorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The present application is directed at inhibition or prevention ofcorrosion in the oil and gas industry.

BACKGROUND

Corrosion of metal surfaces continues to be a problem in the oil and gasindustry. Aqueous liquids are injected into the earth and recovered fromthe earth during subterranean hydrocarbon recovery processes such ashydraulic fracturing (fracking) and tertiary oil recovery. In one ormore such processes, an aqueous liquid called an “injectate” is injectedinto a subterranean formation. Injectates include water, solids,solvents therein or both. In one or more such processes, a water sourcecalled “produced water,” namely, water that flows back from thesubterranean formation, is recovered and collected. Produced waterincludes one or more of injectate, connate (native water present in thesubterranean formation along with the hydrocarbon), sea water, and minor(e.g. less than 5 wt %) amounts of hydrocarbon products, which arehydrocarbon liquids or solids entrained (dispersed, emulsified, ordissolved) in the produced water. The injectate and the produced watercan include “corrodents” such as salts or other dissolved solids,liquids, gases, or combination thereof that cause, accelerate, orpromote corrosion of metal containments that contact the corrodents.These aggressive constituents can cause severe corrosion as evidenced bysurface pitting, embrittlement, and general loss of metal. Corrosionproblems are even more troublesome in deep-sea operations wherereplacement of corroded equipment is difficult and costly. As a result,almost all operators in the oil and gas industry employ corrosioninhibitors to reduce corrosion in metal containments, which contactaqueous liquids containing corrodents.

Governmental regulations imposed on the oil and gas-producing industryhave demanded “greener” chemistries with reduced environmental effects,yet requiring identical performance levels as with existing treatments.

In view of these challenges, improved, and in particular environmentallyfriendly, corrosion inhibitors are desirable.

SUMMARY

Described herein are compositions and methods for inhibiting corrosionin a fluid comprising water, gas, liquid hydrocarbon or combinationthereof.

In one aspect of the invention is a composition comprising at least onealkyl lactone-derived hydroxyamide or alkyl lactone-derived hydroxyesterto inhibit corrosion, the at least one alkyl lactone-derivedhydroxyamide formed by a reaction between an alkyl lactone with anamine, and the alkyl lactone-derived hydroxyester formed by a reactionbetween an alkyl lactone with an alcohol.

In another aspect of the invention is a composition comprising: a fluidsource; and the alkyl lactone-derived hydroxyamide or alkyllactone-derived hydroxyester composition.

In yet another aspect of the invention is a method of inhibitingcorrosion of metal containments in contact with a fluid sourcecomprising the steps of:

introducing into the fluid source a composition comprising at least onealkyl lactone-derived hydroxyamide or alkyl lactone-derivedhydroxyester, the at least one alkyl lactone-derived hydroxyamide formedby a reaction between an alkyl lactone with an amine, and the at leastone alkyl lactone-derived hydroxyester formed by a reaction between analkyl lactone with an alcohol.

The above-described compositions and methods are suitable for use inaquatic environments as they have lower toxicities.

DETAILED DESCRIPTION

Although the present disclosure provides references to variousembodiments, persons skilled in the art will recognize that changes maybe made in form and detail without departing from the spirit and scopeof the invention. Various embodiments will be described in detail withreference to the figures. Reference to various embodiments does notlimit the scope of the claims attached hereto. Additionally, anyexamples set forth in this specification are not intended to be limitingand merely set forth some of the many possible embodiments for theappended claims.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Preferred methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentinvention. All publications, patent applications, patents and otherreferences mentioned herein are incorporated by reference in theirentirety.

As used herein, the term “alkyl” refers to a monovalent group derived bythe removal of a single hydrogen atom from a straight or branched chainor cyclic saturated or unsaturated hydrocarbon containing from one tosixty carbon atoms.

As used herein, the term “corrodents,” are materials that cause,initiate, catalyze, accelerate, induce, or otherwise promote thecorrosion of metals.

As used herein, the term “corrosion inhibitor” (CI) means a compound ormixture that prevents, retards, mitigates, reduces, controls and/ordelays corrosion.

As used herein, the term “fluid source” means any fluid used in oil orgas well production operations that contain one or more corrodents.

As used herein, the term “inhibits,” “inhibiting,” or grammaticalequivalents thereof refer to preventing, retarding, mitigating,reducing, controlling and/or delaying corrosion.

As used herein, the term “injectate” means water plus any solids orliquids dispersed therein that is injected into a subterranean formationfor the purpose of inducing hydrocarbon recovery therefrom. Injectatesoptionally include salts, polymers, surfactants, scale inhibitors,stabilizers, metal chelating agents, corrosion inhibitors, paraffininhibitors, and other additives as determined by the operator in asubterranean hydrocarbon recovery process.

As used herein, the term “produced water” means water that flows backfrom a subterranean reservoir and is collected during a hydrocarbonrecovery process including, but not limited to hydraulic fracturing andtertiary oil recovery. Produced water includes residual hydrocarbonproducts entrained therein and one or more of injectate, connate (nativewater present in the subterranean formation along with the hydrocarbon),brackish water, and sea water. Produced water ranges in temperature fromabout −30° C. to about 200° C., depending on the subterranean reservoirand the terranean environment and infrastructure proximal to thesubterranean reservoir.

As used herein, the terms “comprise(s),” “include(s),” “having,” “has,”“can,” “contain(s),” and variants thereof are intended to be open-endedtransitional phrases, terms, or words that do not preclude thepossibility of additional acts or structures. The singular forms “a,”“and” and “the” include plural references unless the context clearlydictates otherwise. The present disclosure also contemplates otherembodiments “comprising,” “consisting of” and “consisting essentiallyof,” the embodiments or elements presented herein, whether explicitlyset forth or not.

As used herein, the term “optional” or “optionally” means that thesubsequently described event or circumstance may but need not occur, andthat the description includes instances where the event or circumstanceoccurs and instances in which it does not.

As used herein, the term “about” modifying, for example, the quantity ofan ingredient in a composition, concentration, volume, processtemperature, process time, yield, flow rate, pressure, and like values,and ranges thereof, employed in describing the embodiments of thedisclosure, refers to variation in the numerical quantity that canoccur, for example, through typical measuring and handling proceduresused for making compounds, compositions, concentrates or useformulations; through inadvertent error in these procedures; throughdifferences in the manufacture, source, or purity of starting materialsor ingredients used to carry out the methods, and like proximateconsiderations. The term “about” also encompasses amounts that differdue to aging of a formulation with a particular initial concentration ormixture, and amounts that differ due to mixing or processing aformulation with a particular initial concentration or mixture. Wheremodified by the term “about” the claims appended hereto includeequivalents to these quantities. Further, where “about” is employed todescribe a range of values, for example “about 1 to 5” the recitationmeans “1 to 5” and “about 1 to about 5” and “1 to about 5” and “about 1to 5” unless specifically limited by context.

As used herein, the term “substantially” means “consisting essentiallyof” and includes “consisting of” “consisting essentially of” isconstrued as in U.S. patent law, and “consisting of” is construed as inU.S. patent law. For example, a solution that is “substantially free” ofa specified compound or material may be free of that compound ormaterial, or may have a minor amount of that compound or materialpresent, such as through unintended contamination, side reactions, orincomplete purification. A “minor amount” may be a trace, anunmeasurable amount, an amount that does not interfere with a value orproperty, or some other amount as provided in context. A compositionthat has “substantially only” a provided list of components may consistof only those components, or have a trace amount of some other componentpresent, or have one or more additional components that do notmaterially affect the properties of the composition. Additionally,“substantially” modifying, for example, the type or quantity of aningredient in a composition, a property, a measurable quantity, amethod, a value, or a range, employed in describing the embodiments ofthe disclosure, refers to a variation that does not affect the overallrecited composition, property, quantity, method, value, or range thereofin a manner that negates an intended composition, property, quantity,method, value, or range. Where modified by the term “substantially” theclaims appended hereto include equivalents according to this definition.

As used herein, any recited ranges of values contemplate all valueswithin the range and are to be construed as support for claims recitingany sub-ranges having endpoints which are real number values within therecited range. By way of example, a disclosure in this specification ofa range of from 1 to 5 shall be considered to support claims to any ofthe following ranges: 1-5; 1-4; 1-3; 1-2; 2-5; 2-4; 2-3; 3-5; 3-4; and4-5.

Described are compositions and methods to inhibit corrosion of metalcontainments used in liquid hydrocarbon recovery, processing,transportation, and storage operations.

In embodiments, the compounds used in the compositions and methods forinhibiting corrosion are alkyl lactone-derived hydroxyamides, alkyllactone derived-hydroxyesters, or combination thereof. The compounds areformed by the reaction of alkyl lactones and amines, or alkyl lactonesand alcohols. Such alkyl lactone-derived compounds have the generalformula shown below as formula I,

wherein X=nitrogen or oxygen;

wherein R¹=any fatty tail derived from 1-30 carbon saturated orunsaturated alkyl group or a ring structure including cyclohexyl,cyclopentyl, phenyl, benzyl, or variants thereof;

wherein R²=is H or any 1-10 carbon saturated or unsaturated alkyl groupor a ring structure which would link to R³; and

wherein R³=H or any 1-10 carbon saturated or unsaturated alkyl group ora ring structure which would link to R², e.g. pyrrolidine or azepane,and the like.

In embodiments, the alkyl lactone-derived hydroxyamide is shown below asformula II,

III and IV, with the various groups as previously described.

wherein, R¹=any fatty tail derived from 1-30 carbon atom saturated orunsaturated alkyl group or a ring structure including cyclohexyl,cyclopentyl, phenyl, benzyl, or variants thereof;

wherein R²=H or any 1-10 carbon atom saturated or unsaturated alkylgroup or being a ring structure which would link to R³; and

wherein R³=H or any 1-10 carbon atom saturated or unsaturated alkylgroup or being a ring structure which would link to R², e.g. pyrrolidineor azepane, and the like.

In embodiments, R² and R³ are individually selected from isopropyl,butyl, pentyl, isobutyl or isopentyl groups. In embodiments, R² and R³individually may include one or more aminopropylamine chains such asdimethylaminopropylamine (DMAPA) or dibutylaminopropylamine (DBAPA). Inembodiments, R²=R³. In embodiments, R² and R³ are individually derivedfrom the following amines:

Aminopropyl pyrrolidine

Aminopropyl azepane

and

An extended dibutylaminopropylenediamine

In embodiments, the alkyl lactone-derived hydroxyamides include one ormore of the following structures or a combination thereof:

Any suitable method may be used to synthesize the alkyl lactone-derivedhydroxyamides. The synthesis of the alkyl lactone-derived hydroxyamidesis not limited by the described processes.

In embodiments, the alkyl lactone-derived hydroxyamides are obtained byreacting alkyl lactones with amines as shown below, wherein R¹ is analkyl moiety and R² and R³ are selected from H or an alkyl group, withthe proviso that only one of R² and R³ may be H.

In embodiments, the alkyl lactone-derived hydroxyamide is formed byreacting an alkyl lactone and an aminopropyl amine followed byacidification as shown below, wherein, R¹=any fatty tail is derived from1-30 carbon atom saturated or unsaturated alkyl group or a ringstructure including cyclohexyl, cyclopentyl, phenyl, benzyl, or variantsthereof; and wherein R² and R³ are an H or an alkyl group with theproviso that only one of R² and R³ may be H.

In embodiments, the alkyl lactone-derived hydroxyamide is formed byreacting the alkyl lactone, which is a γ-undecalactone and an amine,which is dibutylaminopropylamine. The resultant alkyl lactone-derivedhydroxyamide is followed by acidification with acetic acid:

In embodiments, the alkyl lactone-derived hydroxyamide is the reactionproduct of γ-undecalactone with dibutylamine:

In embodiments, the alkyl lactone is γ-undecalactone reacted withdimethylaminopropyl amine (DMAPA) and acidified (e.g. acetic acid) asfollows:

In embodiments, the alkyl lactone-derived hydroxyamide is a reactionproduct between δ undecalactone and DMAPA.

In embodiments, the alkyl lactone-derived hydroxyamide is a reactionproduct between γ octalactone and DMAPA:

In other embodiments, the alkyl lactone-derived hydroxyamides arereaction products as shown below:

In some embodiments, the compositions and methods useful for inhibitingcorrosion includes an alkyl lactone-derived hydroxyester. Inembodiments, the alkyl lactone-derived hydroxyester is a reactionproduct of an alkyl lactone with an alcohol, and as shown below, whereinR¹ is an alkyl moiety (as described above), and R² is an alkyl group.

In embodiments, the alkyl lactone-derived hydroxyester is the reactionproduct of γ-undecalactone reacted with dibutylaminoethanol, followed byacidification to form the ammonium salt of the tertiary amino moiety:

In embodiments, the hydroxyl of the alkyl lactone-derived hydroxyesteror alkyl lactone-derived hydroxyamide can be further modified. Inembodiments, the resultant hydroxyl is modified by displacing thehydrogen of the hydroxyl to form an O-bonded moiety. Suitable O-bondedmoieties include ether, carboxylic acid, silyl ether, and the like. Inembodiments, suitable O-bonded moieties are shown below, wherein R¹ isas described previously, and R⁴ is alkyl, silyl, carboxyl, and the like.

In embodiments, the O-bonded moiety is the reaction product of the alkyllactone-derived hydroxyamide or alkyl lactone-derived hydroxyester withmaleic anhydride or other anhydride moiety. For example, the alkyllactone-derived hydroxyamide (which is a reaction betweenγ-undecalactone with dibutylaminopropylamine) is further reacted withmaleic anhydride as follows:

In embodiments, the ether is formed from the alkyl lactone-derivedhydroxyamide by reacting with a bromide. In embodiments, the alkyllactone-derived hydroxyamide is formed by reacting γ-undecalactone withDBAPA. The resultant alkyl lactone-derived hydroxyamide is furtherreacted with n-butyl bromide to yield a corresponding ether as follows:

In still other embodiments, the resultant hydroxyl of the alkyllactone-derived hydroxyamide or alkyl lactone-derived hydroxyester ismodified by oxidation to a ketone. For example, oxidation to a ketone isas shown below, wherein R¹ is as described above, and the newly formedketone can be left as-is or further reacted with amines (Schiff baseformation, reductive amination, and the like), or reacted via aldolreactions, Mannich reactions, and the like.

In embodiments, the oxidation can be with yridinium chlorochromate (PCC)to yield a ketone as shown below:

Any suitable alkyl lactones may be used to react with the amine. Inembodiments, the alkyl lactones have at least two carbon atoms in thelactone ring. In embodiments, the lactones are from 2-30 or 5-20 carbonatoms. In embodiments, the alkyl lactones are gamma-alkyl lactones anddelta-alkyl lactones. In embodiments, the alkyl lactones are beta,epsilon, or larger variants such as omega-alkyl lactones (for examplew-pentadecalactone). In embodiments, the variability in the alkyl moietyare at the gamma or delta carbon, but can occur along the alpha, beta,gamma, delta, or epsilon position along the lactone ring, in multiplelocations and chiralities.

In embodiments, the alkyl chain is a straight chain alkyl having 1-30carbon straight or branched chain alkyl. In other embodiments, the alkylchain is a branching, unsaturation or additional functionality. Inembodiments, unsubstituted alkyl groups include methyl, ethyl, n-propyl,i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl,s-pentyl, t-pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, and thelike.

In embodiments, the alkyl lactones are either synthetic or natural. Inembodiments, the synthetic lactones can be produced from fatty acidsplus acrylic acid and peroxide.

In embodiments, the lactones are naturally produced, where they arecommonly used as food additives or flavor/fragrance molecules. Inembodiments, natural lactones include cis-3-methyl-4-octanolide (whiskylactone), massoia lactone (6-Pentyl-5,6-dihydropyran-2-one),5-(cis-3-Hexenyl)dihydro-5-methyl-2(3H)furanone, 4-methyldeca-4-lactone,angelica lactone and the like.

In embodiments, commercially available lactones, for example from SigmaAldrich include 4-methyldeca-4-lactone, whisky lactone,omega-pentadecalactone, and 6-pentyl-5,6-dihydropyran-2-massoia lactone.

Any suitable amine may be used to react with the alkyl lactone. Theamine may be characterized by the presence of at least of at least oneprimary, secondary or tertiary amino group. Suitable amine includesmonoamines, diamines or polyamines.

Examples of suitable monoamines include ethylamine, dimethylamine,diethylamine, n-butylamine, dibutylamine, allylamine, isobutylamine,cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine,N-methyl-octylamine, dodecyl-amine, diethanolamine, morpholine, andoctadecyl amine.

In other embodiments, the amines are diamines, which can includealiphatic diamines, branched aliphatic diamines, cyclic diamines.

In embodiments, the amine dimethylaminopropyl amine.

In embodiments, the amine is a dibutylaminopropylenediamine (DBAPA)

In embodiments, the polyamines have the formula [R⁵—NH—R⁶], wherein R⁵and R⁶ are a H or an alkyl group.

In embodiments, polyamines are used in the preparation of the AA. Inembodiments, polyalkylene polyamines of about 2 to 60, 2 to 40, 3 to 20total carbon atoms and about 1 to 12, 3 to 12, 5 to 9 nitrogen atoms inthe molecule.

In embodiments, amines are hydrocarbyl amines or hydrocarbyl aminesincluding other groups, e.g., hydroxy groups, alkoxy groups, amidegroups, nitriles, imidazoline groups, and the like. Hydroxy amines with1 to 6 hydroxy groups or 1 to 3 hydroxy groups are useful.

In embodiments, amines are aliphatic saturated amines, including thoseof the general formulas:

wherein R, R′, R″ and R′″ are independently selected from a group ofhydrogen; C1 to C25 straight or branched chain alkyl radicals; C1 to C12alkoxy C2 to C6 alkylene radicals; C2 to C12 hydroxy amino alkyleneradicals; and C1 to C12 alkylamino C2 to C6 alkylene radicals; andwherein R′″ can additionally comprise a moiety of the formula:

wherein R′ is as defined above, and wherein s and s′ can be the same ora different number of from 2 to 6, 2 to 4; and t and t′ can be the sameor different and are numbers of from 0 to 10, 2 to 7, or about 3 to 7,with the proviso that the sum oft and t′ is not greater than 15.

In embodiments, exemplary amine compounds include: 1,2-diaminoethane;1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane: polyethyleneamines such as diethylene triamine; triethylene tetramine; tetraethylenepentamine; polypropylene amines such as 1,2-propylene diamine;di-(1,2-propylene)triamine; di-(1,3-propylene) triamine;N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine;N, N-di(2-hydroxyethy 1)-1,3-propylene diamine; 3-dodecyloxypropylamine;N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);diisopropanol amine; diethanol amine; triethanol amine; mono-, di-, andtri-tallow amines; amino morpholines such asN-(3-aminopropyl)morpholine; and mixtures thereof.

In embodiments, the acidification step is of a secondary or tertiaryamine. In embodiments, the acidification is generally achieved throughthe addition of an organic acid. Exemplary organic acids include aceticacid or acrylic acid. In other embodiments, the acrylic acid reactionswith any residual primary or secondary amines (reversibly with tertiaryamines) to yield a carboxybetaine structure. Other organic acids may beused for this acidification, including pivalic acid, malic acid, maleicacid, succinic acid, and any C1-C12+ carboxylic acids. Inorganic acidscan also be used, such as common mineral acids (hydrochloric acid,phosphoric acid, nitric acid, carbonic acid) or related, as well asLewis acids (tetrafluoroborate, aluminum trichloride, or the like).

Any suitable alcohol may be used to react the alkyl lactone to result inthe disclosed alkyl lactone-derived hydroxyester. In embodiments,alcohols having the formula: OH—R⁷ are used, wherein R⁷ is an alkyl,aryl or alkaryl hydrocarbyl group having from one to twenty carbons, andwherein R⁷ may be C1-C20 unsubstituted or substituted alkyl, C2-C20unsubstituted or substituted alkenyl, C2-C20 unsubstituted orsubstituted alkynyl, C3-C20 unsubstituted or substituted cycloalkyl,C3-C20 unsubstituted or substituted cycloalkyl containing at least oneheteroatom, C6-C20 unsubstituted or substituted aryl, C6-C20unsubstituted or substituted aryl containing at least one heteroatom,C7-C20 unsubstituted or substituted alkaryl, or C7-C20 unsubstituted orsubstituted alkaryl containing at least one heteroatom.

In embodiments, the alcohols are methanol, ethanol, propanol,i-propanol, n-butanol, butanol, t-butanol, n-octanol, hexanol,cyclohexanol and benzyl alcohol or combinations thereof. In embodiments,the alcohol is an amino alcohol. Amino alcohols include the2,2-disubstituted-2-amino-1-alkanols having from two to three hydroxygroups and containing a total of 4 to 8 carbon atoms. This amino alcoholcan be represented by the formula:

wherein X is an alkyl or hydroxyalkyl group with the alkyl groups havingfrom 1 to 3 carbon atoms wherein at least one, and preferably both, ofthe X substituents is a hydroxyalkyl group of the structure—(CH₂)_(n)OH, n being 1 to 3.

In embodiments, the alcohols are amino alcohols. Examples of aminoalcohols include 2-amino-2-methyl-1,3 propanediol,2-amino-2-ethyl-1,3-propanediol, and2-amino-2-(hydroxymethyl)1,3-propanediol, (THAM or tris (hydroxymethyl)amino methane). In other embodiments, the alcohol is adibutylaminoethanol, diethylaminoethanol, dipropylaminoethanol,diisopropyl, diisobutyl, diisopentyl, dipentyl and diisohexyl/dihexyl.

The compositions and methods described herein are used to inhibitcorrosion. In embodiments, compositions comprise, consist essentiallyof, or consist of at least one of the described alkyl lactone-derivedhydroxyamides or alkyl lactone-derived hydroxyester used for corrosioninhibition. In embodiments, the alkyl lactone-derived hydroxyamides oralkyl lactone-derived hydroxyesters or compositions containing theminclude other additives such as one or more asphaltene inhibitors,paraffin inhibitors, scale inhibitors, demulsifiers, water clarifiers,dispersants, emulsion breakers, antifoams, or any combination thereof.In embodiments, the alkyl lactone-derived hydroxyamide or alkyllactone-derived hydroxyester further comprises one or more solvents or amixture thereof.

In embodiments, the solvents suitable for formulation with the alkyllactone-derived hydroxyamide or alkyl lactone-derived hydroxyestercomposition are water, brine, seawater, alcohols such as methanol,ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol,t-butanol or higher alcohols such as benzyl alcohol); ketones such asacetone, or methyl ethyl ketone (2-butanone); acetonitrile; esters suchas ethyl acetate, propyl acetate and butyl acetate; ethers such asdiethyl ether or higher, e.g. methyl t-butyl ether, glyme, diglyme,ethylene glycol monobutyl ether, ethylene diglycol ethyl ether, 1,4dioxane and related; aromatics such as toluene, xylene(s),diethylbenzene, naphthalene and related aromatics or refinery cuts(heavy aromatic naptha, heavy aromatic distillates, and related);aliphatics such as pentane, hexane, heptane, octane, or refinedgasoline; or several “green” solvents such as 2-methyltetrahydrofuran,furfural alcohol, and cyclopentylmethylether.

In embodiments, the solvents suitable for formulation with the alkyllactone-derived hydroxyamide or alkyl lactone-derived hydroxyestercomposition are aliphatic, such as pentane, hexane, cyclohexane,methylcyclohexane, heptane, decane, dodecane, diesel, and the like, andaromatics, such as toluene, xylene, heavy aromatic naphtha, fatty acidderivatives (acids, esters, amides), and the like.

In embodiments, the composition can include solvents disclosed in U.S.patent application Ser. No. 15/992,383 filed May 30, 2018.

In embodiments, the the alkyl lactone-derived hydroxyamide or alkyllactone-derived hydroxyester alone or in a composition is used in anamount from about 1 ppm to 10,000 ppm, from about 100 ppm to about 1000,from about 500 ppm to about 3000 ppm, from 750 ppm to 3,000 ppm, fromabout 5000 ppm to about 2,000 ppm, from about 5000 ppm to about 3,000ppm, or 100 ppm to 3,000 ppm.

In embodiments, the composition comprising the alkyl lactone-derivedhydroxyamide or alkyl lactone-derived hydroxyester is used in a methodof inhibiting corrosion in a fluid source. The fluid source can becontained in a metal container or in contact with pipelines used totransport fluid sources toward, into, out of a subterranean formation.In embodiments, the corrodents include hydrogen sulfide, carbon dioxide,oxygen, sodium chloride, calcium chloride, sulfur dioxide, orcombination thereof. In embodiments, the fluid source comprises water,gas, and optionally liquid hydrocarbon or combination thereof. Inembodiments, the fluid source is produced water or an injectate.

In embodiments, various dosage amounts of the composition and/or the thealkyl lactone-derived hydroxyamide or alkyl lactone-derived hydroxyesterare introduced to a fluid source to inhibit corrosion of a metalcontainment in contact with the fluid source. One of ordinary skill inthe art is able to calculate the amount of alkyl lactone-derivedhydroxyamide or alkyl lactone-derived hydroxyester or compositioncomprising alkyl lactone-derived hydroxyamide or alkyl lactone-derivedhydroxyester for a given situation without undue experimentation.Factors that would be considered important in such calculations include,for example, content of fluid source, content of corrodents, percentagewater cut, and similar parameters.

In some embodiments, the composition comprising the alkyllactone-derived hydroxyamide or alkyl lactone-derived hydroxyester isapplied to a fluid source that contains various levels of water cut. Oneof ordinary skill in the art understands that “water cut” refers to the% of water in an oil and water mixture. In one embodiment, the water cutis from about 1% to about 80% w/w with respect to the hydrocarbon phase.In other embodiments, the water cut is from about 1% to about 30% w/w,from about 5% to about 40% w/w, from about 10% to about 60% w/w, fromabout 15% to about 80% w/w with respect to the hydrocarbon phase.

In embodiments, the composition comprising the alkyl lactone-derivedhydroxyamide or alkyl lactone-derived hydroxyester is applied to a fluidsource that contains various levels of salinity. In one embodiment, thefluid source has a salinity of about 0.1% to about 25% or about 10% toabout 25% weight/weight (w/w) total dissolved solids.

The alkyl lactone-derived hydroxyamide or alkyl lactone-derivedhydroxyester may be introduced into a fluid source by any means suitablefor ensuring dispersal of the alkyl lactone-derived hydroxyamide oralkyl lactone-derived hydroxyester through the fluid source beingtreated. The composition comprising the alkyl lactone-derivedhydroxyamide or alkyl lactone-derived hydroxyester can be injected asprepared or formulated in one or more additional solvents, dependingupon the application and requirements. One of skill in the art willunderstand that the methods disclosed herein are not limited in any wayby the timing or location of the introduction.

In embodiments, the alkyl lactone-derived hydroxyamide or alkyllactone-derived hydroxyester are introduced to a fluid using variouswell-known methods and they may be introduced at numerous, differentlocations throughout a given system. In one embodiment, the compositioncomprising the alkyl lactone-derived hydroxyamide or alkyllactone-derived hydroxyester is pumped into an oil/gas pipeline using anumbilical line. In some embodiments, capillary string injection systemsmay be utilized to deliver the composition. U.S. Pat. No. 7,311,144provides a description of an apparatus and methods relating to capillaryinjection, the disclosure of which is incorporated into the presentapplication in its entirety. In other embodiments, the compositioncomprising the one or more alkyl lactone-derived hydroxyamide or alkyllactone-derived hydroxyester is injected using mechanical equipment suchas chemical injection pumps, piping tees, injection fittings, and thelike.

Introducing may be achieved also by mixing, blending with mechanicalmixing equipment or devices, stationary mixing setup or equipment,magnetic mixing or other suitable methods, other equipment and meansknown to one skilled in the art and combinations thereof to provideadequate contact and/or dispersion of the composition into the fluidsource. The contacting can be made in-line and/or offline. The variouscomponents of the composition may be mixed prior to and/or duringcontact. If needed or desired, the composition or some of its componentsmay be optionally removed or separated mechanically, chemically, or byother methods known to one skilled in the art.

In embodiments, the alkyl lactone-derived hydroxyamide or alkyllactone-derived hydroxyester described herein have increasedbiodegradation, lower toxicity, lower bioaccumulation or combinationthereof. In embodiments, the alkyl lactone-derived hydroxyamide or alkyllactone-derived hydroxyester have a biodegradation of greater than 10%,greater than 20%, greater than 30%, greater than 40%, greater than 50%or greater than 60% when measured in a 28 day degradation test.

In embodiments, the alkyl lactone-derived hydroxyamide or alkyllactone-derived hydroxyester have reduced toxicity as measured in a 48hour acute toxicity test with Daphnia magna. In embodiments, the alkyllactone-derived hydroxyamide or alkyl lactone-derived hydroxyester has a48-hour EC₅o value with Daphnia magna of greater than or equal to 10mg/ml. In embodiments, the alkyl lactone-derived hydroxyamide or alkyllactone-derived hydroxyester has a 48-hour EC₅o value with Daphnia magnafrom about 10-100 mg/ml, 10-20 mg/ml, 15-25 mg/ml, 20-35 mg/ml, 30-40mg/ml, 35-50 mg/ml, 40-60 mg/ml, 50-80 mg/ml, 60-90 mg/ml, or 70-100mg/ml.

Some additional non-limiting embodiments are provided below to furtherexemplify the present disclosure:

Embodiment 1

A composition comprising at least one alkyl lactone-derived hydroxyamideor alkyl lactone-derived hydroxyester to inhibit corrosion, the at leastone alkyl lactone-derived hydroxyamide formed by a reaction between analkyl lactone with an amine, and the alkyl lactone-derived hydroxyesterformed by a reaction between an alkyl lactone with an alcohol.

Embodiment 2

The composition of embodiment 1, wherein the alkyl lactone comprises a 2to 30 carbon atom-containing lactone.

Embodiment 3

The composition as in one of embodiments 1-2, wherein the alkyl lactonecomprises a 1-30 carbon atom-containing alkyl substituent.

Embodiment 4

The composition of embodiment 1, wherein the alkyl lactone is a 6undecalactone, a γ undecalactone or a γ octalactone.

Embodiment 5

The composition as in one of embodiments 1-4, wherein the aminecomprises a primary, secondary or tertiary amine.

Embodiment 6

The composition as in one of embodiments 1-5, wherein the amine is adimethylaminopropylamine.

Embodiment 7

The composition as in one of embodiments 1-6, wherein the alkyllactone-derived hydroxyamide comprises:

Embodiment 8

The composition as in one of embodiments 1-4, wherein the alcohol is anamino alcohol.

Embodiment 9

The composition as in one of embodiments 1-8, wherein the compositionfurther comprises one or more asphaltene inhibitors, paraffininhibitors, scale inhibitors, emulsifiers, water clarifiers,dispersants, emulsion breakers, or any combination thereof.

Embodiment 10

The composition as in one of embodiments 1-9, wherein the alkyllactone-derived hydroxyamide or alkyl lactone-derived hydroxyestercomprises a reduced toxicity compared to compositions not containingalkyl lactone derived hydroxyamide or alkyl lactone-derivedhydroxyester.

Embodiment 11

The composition as in one of embodiments 1-10, wherein the alkyl lactonederived hydroxyamide or alkyl lactone-derived hydroxyester comprises aEC₅o value with Daphnia magna greater than or equal to 10 mg/ml.

Embodiment 12

The composition as in one of embodiments 1-11, wherein the alkyl lactonederived hydroxyamide or alkyl lactone-derived hydroxyester comprises a48-hour EC₅o value with Daphnia magna from about 10-100 mg/ml.

Embodiment 13

The composition as in one of embodiments 1-12, wherein the alkyl lactonederived hydroxyamide or alkyl lactone-derived hydroxyester has anincreased biodegradation compared to non-alkyl lactone-derived corrosioninhibitors.

Embodiment 14

The composition as in one of embodiments 1-13, wherein the compositionhas biodegradation of greater than 10%, greater than 20%, greater than30%, greater than 40%, greater than 50%, or greater than 60% whenmeasured in a 28 day degradation test.

Embodiment 15

A composition comprising:

A fluid source; and

-   -   the alkyl lactone-derived hydroxyamide or alkyl lactone-derived        hydroxyester composition as in one of embodiments 1-14.

Embodiment 16

The composition as in one of embodiments 1-17, wherein the the alkyllactone-derived hydroxyamide or alkyl lactone-derived hydroxyester isabout is about 1 ppm to 10,000 ppm by weight.

Embodiment 17

The composition as in one of embodiments 15-17, wherein the fluid sourceis produced water or injectate.

Embodiment 18

The composition as in one of embodiments 15-18, wherein the fluid sourcecomprises water, gas, and optionally liquid hydrocarbon.

Embodiment 19

A method of inhibiting corrosion of metal containments in contact with afluid source comprising the steps of:

-   -   introducing into the fluid source a composition comprising at        least one alkyl lactone-derived hydroxyamide or alkyl        lactone-derived hydroxyester, the at least one alkyl        lactone-derived hydroxyamide formed by a reaction between an        alkyl lactone with an amine, and the at lease one alkyl        lactone-derived hydroxyester formed by a reaction between an        alkyl lactone with an alcohol.

Embodiment 20

The method of embodiment 19, wherein introducing is by injecting orpumping.

Embodiment 21

The method as in one of embodiments 19-20, wherein the fluid source iscontained in an oil or gas pipeline or refinery.

Embodiment 22

The method as in one of embodiments 19-21, wherein the fluid sourcecomprises water, gas, optionally liquid hydrocarbon or combinationthereof.

Embodiment 23

The method as in one of embodiments 19-22, wherein the fluid sourcecomprises about 0.1% to about 25% weight/weight total dissolved solids.

Embodiment 24

The method as in one of embodiments 19-23, wherein the fluid compriseswater of about 1% to about 80% weight/weight with respect to thehydrocarbon phase.

Embodiment 25

The method as in one of embodiments 19-24, wherein the alkyl lactonecomprises a 2 to 30 carbon atom-containing lactone.

Embodiment 26

The method as in one of embodiments 19-25, wherein the alkyl lactonecomprises a 1-30 carbon atom-containing alkyl substituent.

Embodiment 27

The method as in one of embodiments 19-26, wherein the alkyl lactone isa 6 undecalactone, a γ undecalactone or a γ octalactone.

Embodiment 28

The method as in one of embodiments 19-27, wherein the amine comprises adimethyl aminopropylamine.

Embodiment 29

The method as in one of embodiments 19-28, wherein the reaction productcomprises:

Embodiment 30

The method as in one of embodiments 19-27, wherein the alcohol is anamino alcohol.

Embodiment 31

The method as in one of embodiments 19-30, wherein the alkyllactone-derived hydroxyamide or alkyl lactone-derived hydroxyester hasthe general formula:

wherein X=nitrogen or oxygen;

wherein R¹=any fatty tail derived from 1-30 carbon saturated orunsaturated alkyl group or a ring structure including cyclohexyl,cyclopentyl, phenyl, benzyl, or variants thereof;

wherein R²=is H or any 1-10 carbon saturated or unsaturated alkyl groupor a ring structure which would link to R³; and

wherein R³=H or any 1-10 carbon saturated or unsaturated alkyl group ora ring structure which would link to R².

Embodiment 32

Use of the alkyl lactone-derived hydroxyamide or alkyl lactone-derivedhydroxyester as in one of embodiments 1-31 to inhibit corrosion.

EXAMPLES

The following examples are intended to illustrate different aspects andembodiments of the invention and are not to be considered limiting thescope of the invention. It will be recognized that various modificationsand changes may be made without following the experimental embodimentsdescribed herein, further without departing from the scope of theclaims.

Example 1

γ-undecalactone/DMAPA

In a 40 mL, Teflon top vial was weighed 5.0 g of γ-undecalactone and2.77 g of dimethylaminopropylamine (1 eq). A stir bar was added and theflask was set to stir at 50° C. for 4 hours. Once the reaction wascomplete, the contents were allowed to return to room temperature and1.62 g acetic acid (1.0 eq) was added to the contents. Finally, thecontents were diluted to 50 wt % active in methanol.

δ-undecalactone/DMAPA

In a 40 mL, Teflon top vial was weighed 5.0 g of 6-undecalactone and2.77 g of dimethylaminopropylamine (1 eq). A stir bar was added and theflask was set to stir at 50° C. for 4 hours. Once the reaction wascomplete, the contents were allowed to return to room temperature and1.62 g acetic acid (1.0 eq) was added. Finally, the contents werediluted to 50 wt % active in methanol.

γ-octalactone/DMAPA

In a 40 mL, Teflon top vial was weighed 2.0 g of γ-octalactone and 1.437g of dimethylaminopropylamine (1 eq). A stir bar was added and the flaskwas set to stir at 50° C. for 4 hours. Once the reaction was complete,the contents were allowed to return to room temperature and 0.845 gacetic acid (1.0 eq) was added to the contents. Finally, the contentswere diluted to 50 wt % active in methanol.

Example 2

The bubble cell test was used to investigate the effectiveness of alkyllactone-derived hydroxyamides as corrosion inhibitors. This testmeasures the corrosion rate of a steel electrode by aqueous linearpolarization resistance (LPR). The steel electrodes (C1018) were placedin a bath of synthetic oilfield brine which was deaerated with carbondioxide. The corrosion rate of the electrode was compared in the absenceor presence of an alkyl lactone-derived hydroxyamide.

The synthetic oilfield brine contained about 3 wt % of sodium chloride,and the oil included a synthetic oil of LVT-200 and xylene. The ratio ofwater to oil was 80:20. The oil/brine was placed into bubble cells andpurged with CO₂. The oil/brine was continually purged with CO₂ tosaturate the oil/brine prior to starting the test. The test cells wereblanketed with CO₂ throughout the duration of the test to maintainsaturation. The bubble cells were stirred at 100 revolutions per minute(rpm) for the duration of the test to maintain thermal equilibrium at80° C. The electrodes were all cleaned and polished prior to testing.Details of the test are shown in Table 1.

TABLE 1 Test Conditions Temperature (° C.) 80 Water Cut (%) 80 Oil Type75% LVT-200, Xylene 25% Stirrer Speed (rpm) 100  Purge Gas CO2 CO₂pressure Ambient H₂S (ppm)  0 Electrode Material C1018

After about 3 hours of pre-corrosion time (i.e. without a corrosioninhibitor) 10 ppm of a 20% active of an alkyl-lactone chemistry (shownin Table 2 and prepared as described in Example 1) with 2%2-mercaptoethanol (2ME) solvent was added. Comparison with a benzylammonium chloride quaternary chemistry and imidazoline chemistry wasmade at the same active concentration as the alkly lactone together with2ME (at the same dose based on chemistry and 2ME activity—i.e. thesewere dosed at twice the concentration because the active and 2ME in thetest blend was half).

The bubble cells were dosed with the various samples shown in Table 2.

TABLE 2 Sample Chemistry Blank brine and synthetic oil without acorrosion inhibitor Comparative sample A standard benzyl ammoniumchloride quaternary chemistry Comparative sample B TOFA:DETA imidazolinesalted with acetic acid Sample 1 γ undecalactone + dimethylaminopropylamine (DMAPA) conjugate + acetic acid. Sample 2 δ undecalactone +dimethylaminopropyl amine (DMAPA) conjugate + acetic acid Sample 3 γoctalactone + dimethylaminopropyl amine (DMAPA) conjugate + acetic acid.

The results are shown in Table 3. In the presence of the sameconcentration of both active chemistry and synergist, the resultanthydroxyamide, which is a reaction between δ undecalactone,dimethylaminopropyl amine (DMAPA)+acetic acid chemistry (Sample 2)outperformed the standard benzyl ammonium chloride quaternary chemistry(Comparative Sample A) in which a 43% corrosion inhibition was gainedfor Sample 2 compared with 38% inhibition for Comparative Sample A.Sample 2 provided similar performance to the standard imidazolinechemistry, which also provided a 43% inhibition.

Sample 1 and Sample 3 showed similar results as the Comparative SampleA.

TABLE 3 15 h after dosing Candidate Baseline Inhibited ChemistryCorrosion Corrosion Candidate Activity Dosage Rate Rate % ChemicalChemistry Synergist (%) (ppm) (mpy) (mpy) Protection Blank N/A N/A N/A 0260 500 −92 Comparative Dimethyl benzyl 1% 2ME 10 20 236 147 38 sample Aammonium chloride quaternary (% n- Alkyl (5% C12, 60% C14, 30% C16, 5%C18) Comparative TOFA:DETA 1% 2ME 10 20 245 141 43 sample B imidazolinesalted with acetic acid Sample 1 γ undecalactone/ 2% 2ME 20 10 289 18137 DMAPA + acetic acid Sample 2 δ undecalactone/ 2% 2ME 20 10 266 151 43DMAPA + acetic acid Sample 3 γ octalactone/ 2% 2ME 20 10 255 177 31DMAPA) + acetic acid

What is claimed is:
 1. A composition comprising at least one alkyllactone-derived hydroxyamide or alkyl lactone-derived hydroxyester toinhibit corrosion, the at least one alkyl lactone-derived hydroxyamideformed by a reaction between an alkyl lactone with an amine, and thealkyl lactone-derived hydroxyester formed by a reaction between an alkyllactone with an alcohol.
 2. The composition of claim 1, wherein thealkyl lactone comprises a 1-30 carbon atom-containing alkyl substituent.3. The composition of claim 1, wherein the alkyl lactone is a δundecalactone, a γ undecalactone or a γ octalactone.
 4. The compositionof claim 1, wherein the amine is a dimethylaminopropylamine.
 5. Thecomposition of claim 1, wherein the alkyl lactone-derived hydroxyamidecomprises:


6. The composition of claim 1, wherein the composition further comprisesone or more asphaltene inhibitors, paraffin inhibitors, scaleinhibitors, emulsifiers, water clarifiers, dispersants, emulsionbreakers, or any combination thereof.
 7. The composition of claim 1,wherein the alkyl lactone-derived hydroxyamide or alkyl lactone-derivedhydroxyester comprises a reduced toxicity compared to compositions notcontaining alkyl lactone derived hydroxyamide or alkyl lactone-derivedhydroxyester.
 8. The composition of claim 1, wherein the alkyl lactonederived hydroxyamide or alkyl lactone-derived hydroxyester comprises aEC₅o value with Daphnia magna greater than or equal to 10 mg/ml.
 9. Thecomposition of claim 1, wherein the alkyl lactone derived hydroxyamideor alkyl lactone-derived hydroxyester comprises a 48-hour EC₅o valuewith Daphnia magna from about 10-100 mg/ml.
 10. The composition of claim1, wherein the alkyl lactone derived hydroxyamide or alkyllactone-derived hydroxyester has an increased biodegradation compared tonon-alkyl lactone-derived corrosion inhibitors.
 11. The composition ofclaim 1 comprising: a fluid source; and the alkyl lactone-derivedhydroxyamide or alkyl lactone-derived hydroxyester, wherein the fluidsource comprises wherein the fluid source comprises water, gas, andoptionally liquid hydrocarbon.
 12. A method of inhibiting corrosion ofmetal containments in contact with a fluid source comprising the stepsof: introducing into the fluid source a composition comprising at leastone alkyl lactone-derived hydroxyamide or alkyl lactone-derivedhydroxyester, the at least one alkyl lactone-derived hydroxyamide formedby a reaction between an alkyl lactone with an amine, and the at leastone alkyl lactone-derived hydroxyester formed by a reaction between analkyl lactone with an alcohol.
 13. The method of claim 12, wherein thefluid source is contained in an oil or gas pipeline or refinery.
 14. Themethod of claim 12, wherein the alkyl lactone comprises a 2 to 30 carbonatom-containing lactone.
 15. The method of claim 12, wherein the alkyllactone comprises a 1-30 carbon atom-containing alkyl substituent. 16.The method of claim 12, wherein the alkyl lactone is a 6 undecalactone,a γ undecalactone or a γ octalactone.
 17. The method of claim 12,wherein the amine comprises a dimethyl aminopropylamine.
 18. The methodof claim 12, wherein the reaction product comprises:


19. The method of claim 12, wherein the alkyl lactone-derivedhydroxyamide or alkyl lactone-derived hydroxyester has the generalformula:

wherein X=nitrogen or oxygen; wherein R¹=any fatty tail derived from1-30 carbon saturated or unsaturated alkyl group or a ring structureincluding cyclohexyl, cyclopentyl, phenyl, benzyl, or variants thereof;wherein R²=is H or any 1-10 carbon saturated or unsaturated alkyl groupor a ring structure which would link to R³; and wherein R³=H or any 1-10carbon saturated or unsaturated alkyl group or a ring structure whichwould link to R².